Thesis (MSc (Chemistry and Polymer Science))--University of Stellenbosch, 2010. / ENGLISH ABSTRACT: See full text for abstract / AFRIKAANSE OPSOMMING: Sien volteks vir opsomming

Thesis (MSc)--Stellenbosch University, 2013. / ENGLISH ABSTRACT: In this thesis we describe various attempts at incorporating macrocycles into dendritic architectures to form macrocycle-dendrimer conjugates with the aim of preparing materials that would exhibit properties that are more than the sum of the constituent parts, in this case macrocycles and dendrimers. A further aim was the synthesis and characterization of metallodendrimers based on such scaffolds and to test these as catalyst precursors in the catalytic oxidation of alcohols. The synthesis of two different types of conjugate systems was attempted; viz. dendrimers functionalized with macrocycles on the peripheries and dendrimers with macrocyclic cores. The synthesis of conjugate systems based on cyclam as the macrocycle was attempted. This required the mono functionalization of cyclam with a linker molecule capable of further reaction with the functional groups at the periphery of commercially available N,N,N,N-tetrakis(3-aminopropyl)-1,4-butanediamine dendrimer. Several approaches were taken in trying to make such conjugate systems but they were not entirely successful. One of the major issues was the final deprotection step, of the Boc-protected cyclam units which proved difficult in our hands. Another approach to prepare the target conjugates involved the use of click chemistry in order to synthesize a dendrimer with an aromatic core and cyclam peripheries. A dendrimer with Boc-protected cyclam peripheries that are bonded through triazole groups to the aromatic core was synthesized. However, subsequent attempts at de-protection of the cyclam functionalities of this conjugate failed to yield the pure de-protected dendrimer. Greater success was achieved with the preparation of a dendrimer with a macrocyclic core. A cyclam cored dendrimer with salicylaldimine peripheries was successfully synthesized and characterized. This dendritic ligand was complexed to Cu(II), Ni(II) and Zn(II) metal ions respectively to form a series of new metallodendrimers. These metallodendrimers were fully characterized using a range of analytical techniques including FT-IR spectroscopy, mass spectrometry, elemental analysis, thermogravimetric analysis, magnetic susceptibility measurements and NMR spectroscopy where appropriate. The Cu(II) and Ni(II) metallodendrimers were tested as catalyst precursors in the catalytic oxidation of benzyl alcohol to benzaldehyde. The catalytic system consisted of the appropriate metallodendrimer, the free radical, 2,2,6,6-tetramethylpiperidinyl- 1-oxyl (TEMPO) and O2 as the oxidant. The reaction parameters, namely the nature of the solvent, catalyst loading, substrate concentration and reaction temperature were sequentially optimized to achieve the best catalytic efficiency. The Cu(II) catalyst precursor exhibited relatively high catalytic activity and achieved TOF’s between 40 and 30 when operating under the optimized conditions, while the Ni(II) catalytic system showed very poor catalytic activity. / AFRIKAANSE OPSOMMING: In hierdie tesis beskryf ons pogings om makroringe in die dendritiese argitektuur te inkorporeer om makroring-dendrimeer gekonjugeerdes te vorm met die hoop dat sulke molekules eienskappe sal toon wat meer is as die somtotaal van die afsonderlike eenhede. ‘n Verdere doel was die sintese en karakterisering van metallodendrimere gebaseer op sulke draers sowel as die toetsing van hierdie molekules as pre-katalisore in die katalitiese oksidasie van alkohole. Pogings tot die sintese van twee verskillende tipes makroring-dendrimeer gekonjugeerdes word beskryf naamlik, dendritiese ligande met makroringe by die buiterand sowel as dendritiese ligande met ‘n makroring as kern word bespreek. Die sintese van makroring-dendrimeer gekonjugeerdes gebasseer op die makroring cyclam word beskryf. Hierdie sintese vereis die gebruik van ‘n monogefunksioneerde cyclam wat ‘n gepaste koppelingsgroep besit. Hierdie koppelingsgroep kan dan verder met funksionele groepe op die oppervlak van die kommersieel beskikbare DAB-dendrimeer reageer. Verskeie pogings is aangewend om sulke gekonjugeerde stelsels te sintetiseer maar hierdie pogings was nie volkome suksesvol nie. ‘n Groot uitdaging was die gebruik en gevolglike latere verwydering van beskermende groepe soos Boc. ‘n Ander benadering het gebruik gemaak van “click” chemie met die doel om ‘n dendrimeer bestaande uit ‘n aromatiese kern en cyclam periferie te vorm. ‘n Dendrimeer met Boc beskermde cyclam eenhede op die buiterand geheg aan ‘n aromatiese kern deur triasool groepe is gesintetiseer. Die verwydering van die beskermende groepe geheg aan die cyclam eenhede was egter weereens ‘n probleem en hierdie metode kon nie die suiwer dendrimeer lewer nie. Groter sukses is behaal met die sintese van ‘n dendrimeer met ‘n cyclam kern en salisielaldimien periferieë. Die dendritiese ligand is vervolgens met metaalsoute van Cu(II), Ni(II) en Zn(II) gereageer om verskeie multikern metaalkomplekse te vorm. Die metaalkomplekse is volledig gekarakteriseer deur verskeie analitiese tegnieke insluitende infrarooi spektroskopie, massa spektrometrie, termografiese analiese, mikroanaliese asook KMR spektroskopie waar moontlik. Die Cu(II) en Ni(II) metaalkomplekse is geëvalueer as pre-katalisatore in die katalitiese oksidasie van alkohole. Hierdie katalitiese sisteem bestaan uit die metaalkompleks, die radikaal TEMPO en molekulêre suurstof. Die invloed van verskeie reaksie- parameters soos die tipe oplosmiddel, die hoeveelheid katalisator, die konsentrasie van die alkohol asook die temperatuur is ondersoek. Gevolglik is die optimale kondisies bepaal om die hoogste opbrengs van bensaldehied te lewer. Die Cu(II) kompleks het ‘n relatief hoë omset van bensielalkohol na bensaldehied getoon met omset frekwensie waardes tussen 30 en 40 onder die optimale kondisies. Die Ni(II) kompleks het egter swak aktiwiteit getoon vir hierdie transformasie.

Nouveaux polymères avec une structure arborescente unique, les dendrimères suscitent un grand intérêt auprès des chercheurs de tous les domaines scientifiques confondus et spécialement auprès des biologistes. Théoriquement synthétisés de façon à ce qu’ils soient parfaitement mono disperses en taille et en masse et de forme sphérique, les dendrimères PAMAM ont des propriétés structurales qui pourraient donner de bons résultats lors de leur utilisation comme vecteurs de médicaments ou d’acides nucléiques.De récentes études biologiques ont montré que les dendrimères PAMAM pouvaient transfecter un grand nombre de cellules de différente nature. Les propriétés structurales et physicochimiques du dendrimère joueraient un rôle essentiel dans l’efficacité de cette transfection et pouvoir prédire ces propriétés permettraient de mieux contrôler le comportement de ces«vecteurs-médicaments» dans l’organisme / In the context of securing clinical gene transfer, new strategies are developed with the creationof synthetic gene vectors based on cationic polymers to replace commonly used viral vectors ingene therapy. PAMAM dendrimers are highly branched macromolecules with controlled nearmonodisperse three-dimensional architecture emanating from a central core. Polymer growthstarts from a central core molecule and growth occurs in an outward direction by a series ofpolymerisation reactions. Hence, precise control over size can be achieved by the extent ofpolymerisation, starting from a few nanometers. Cavities in the core structure and folding of thebranches create cages and channels. The surface groups of dendrimers are amenable tomodification and can be tailored for specific applications. Therapeutic and diagnostic agents areusually attached to surface groups on dendrimers by chemical modification.Recent biological studies have shown that PAMAM dendrimers could transfect a large numberof cells of different nature. The structural properties and physico-chemical properties ofdendrimer play a key role in the efficiency of transfection and to predict these properties wouldbetter control the behavior of these "drug delivery systems in the body.

The preparation of the shape-persistent carbosilane-functionalized porphyrins H2TPP(4-SiRR’Me)4, Zn(II)- TPP(4-SiRR’Me)4 (R = R’ = Me, CH2CHvCH2, CH2 CH2CH2OH; R = Me, R’ = CH2 CHvCH2, CH2CH2CH2OH; TPP = tetraphenyl porphyrin), H2TPP(4-Si(C6H4-1,4-SiRR’Me)3)4, and Zn(II)-TPP(4-Si- (C6H4-1,4-SiRR’Me)3)4 (R = R’ = Me, CH2CHvCH2; R = Me, R’ = CH2CHvCH2) using the Lindsey condensation methodology is described. For a series of five samples their structures in the solid state were determined by single crystal X-ray structure analysis. The appropriate 0th and 1st generation porphyrin-based 1,4-phenylene carbosilanes form 2D and 3D supramolecular network structures, primarily controlled by either π–π interactions (between pyrrole units and neighboring phenylene rings) or directional molecular hydrogen recognition and zinc–oxygen bond formation in the appropriate hydroxyl-functionalized molecules. UV-Vis spectroscopic studies were carried out in order to analyze the effect of the dendritic branches on the optical properties of the porphyrin ring. / Dieser Beitrag ist aufgrund einer (DFG-geförderten) Allianz- bzw. Nationallizenz frei zugänglich.

Dendrimers are a class of polymers with a highly branched, three-dimensional architecture composed of an initiator core, several interior layers of repeating units and multiple surface groups. They have been recognized as the most versatile compositionally and structurally controlled nanoscale building blocks throughout the fields of engineering, materials science, chemistry, and biology, and they have been widely investigated for drug and gene delivery. Polyamidoamine (PAMAM) dendrimers have inherent properties for gene delivery because of their high buffering capacity, polycationic surface and numerous surface groups for biofunctionlization. This dissertation is organized into four independent sections. The first section investigates a series of polyamidoamine-polyethylene glycol-poly (D,L-lactide) (G3.0- PEG1500-PDLLA, G3.0-PEG6000-PDLLA, and G3.0-PEG12000-PDLLA) for gene delivery. Western Blot, fluorescence microscopy and flow cytometry were used as analysis methods. According to gene transfection studies, G3.0-PEG1500-PDLLA has been shown to be capable of inducing higher gene expression than the parent dendrimer compared to unmodified dendrimer, G3.0-PEG6000-PDLLA and G3.0-PEG12000- PDLLA. The second section aims to evaluate an epidermal growth factor (EGF)-containing PAMAM G4.0 dendrimer vector labeled with quantum dots for targeted imaging and nucleic acid delivery. Targeting efficiency, cell viability, proliferation, and intracellular signal transduction were evaluated. We found that EGF-conjugated dendrimers did not stimulate growth of epidermal growth factor receptor (EGFR)-expressing cells at the selected concentration. Consistent with this, minimal stimulation of post-receptor signaling pathways was observed. These nanoparticles can localize within cells that express the EGFR in a receptor-dependent manner, whereas uptake into cells lacking the receptor was low. Vimentin short hairpin RNA (shVIM) and yellow fluorescent protein (YFP) small interfering RNA (siRNA) were used to test the delivery and transfection efficiency of the constructed targeted vector. Significant knockdown of expression was observed, indicating that this vector is useful for introduction of nucleic acids or drugs into cells by a receptor-targeted mechanism. The third section introduces PEGylated polyamidoamine (PAMAM) dendrimer G4.0 conjugates with a novel bis-aryl hydrazone (BAH) linkage for gene delivery. It was found that the incorporation of BAH linkages into the vector significantly enhanced the buffering capacity of the vector with a high degree of PEGylation. According to gene transfection studies, this new vector has been shown to be capable of both transfecting more cells and inducing higher gene expression than the parent dendrimer. This work demonstrates that the use of the BAH linkage in coupling of PEG to the dendrimer helps maintain or increase the buffering capacity of the functionalized dendrimer and results in enhanced transfection. In the fourth section, we explored PAMAM dendrimer G4.5 as the underlying carrier to construct central nervous system (CNS) therapeutic nanoparticles and tested the buccal mucosa as an alternative absorption site for administration of the dendritic nanoparticles. Opioid peptide DPDPE was chosen as a model CNS drug. It was coupled to PAMAM dendrimer G4.5 with PEG or with PEG and transferrin receptor monoclonal antibody OX26. The therapeutic dendritic nanoparticles labeled with 5-(aminoacetamido) fluorescein (AAF) or fluorescein isothiocyanate (FITC) were studied for transbuccal transport using a vertical Franz diffusion cell system mounted with porcine buccal mucosa. Coadministration of bile salt sodium glycodeoxycholate (NaGDC) or application of mucoadhesive gelatin/PEG semi-interpenetrating network (sIPN) enhanced the permeability of dendritic nanoparticles by multiple folds. These results indicate that transbuccal delivery is a possible route for administration of CNS therapeutic nanoparticles. In summary, enhanced nucleic acids delivery by biofunctionalized PAMAM dendrimers was demonstrated. Transbuccal delivery of CNS therapeutic dendritic nanoparticles was demonstrated. These vectors will be useful in gene and drug delivery and could be extended to covalently conjugate other functional moieties for gene and drug delivery.

Anticancer therapeutics are often limited to suboptimal doses due to their lack of selectivity for tumor cells and resultant damage to healthy tissue. These limitations motivated researchers to develop tumor-specific delivery systems for improved therapeutic efficacy and reduced unintended cytotoxicity. Polyamidoamine dendrimers offer an ideal platform for designing targeted therapeutics with tunable characteristics that optimize pharmacokinetic behavior and targeting specificity. Ligand conjugation to dendrimer provides the biochemical interaction necessary to activate tumor-specific receptors for receptor-mediated endocytosis and effective internalization of polyplexes. Tumor-specific receptors overexpressed in carcinomas, like folate receptor-alpha (FOLRα), are targeted by ligand-conjugated dendrimer to allow enhanced internalization of dendrimer and its therapeutic cargo. We examined the cellular trafficking dynamics and potential of folate-conjugated dendrimer for nucleic acid delivery in vitro. Results show folate-conjugation to G4 PAMAM dendrimer (G4FA) confers enhanced uptake in FOLRα-positive tumor cells. Cells internalize G4FA in a receptor-dependent manner with specificity for FOLRα-positive tumor cells.

Projet de thèse consiste de plusieurs parties:-synthèse de nanographène chirale, caractérisation de ses propriétés photo-physiques (publication en JACS acceptée);-synthèse des astérisques moléculaires, qui combinent les propriétés luminescences du noyau benzène persulfuré et des solubilité aqueuse et biocompatibilité des dendrons avec des branches de PEG; une application de ces dendrons pour couvrir les nanoparticules de silice ;-synthèse des astérisques moléculaires avec noyau de benzène persulfuré et branches des heterocycles, pour explorer leurs auto-assemblage et propriétés chelatantes vers métaux. / The synthesis of molecular asterisks as "smart sensors" with a persulfurated benzene core and various ligands was explored. Asterisks with heteroaromatic ligands were synthesized for exploring their metal ions complexing ability. PEG dendrons were tested for increasing the water solubility of the asterisks, and to verify if PEG asterisks could encapsulate some hydrophobic molecules. The PEG dendrons were synthesized for making smart asterisks sensors, and for another purpose: the coating of silica nanoparticles to prevent their fast degradation in water. Unfortunately, this protection from degradation was ineffective, but we could make PEG asterisks to encapsulate molecules (Nile Red) toward new drug nanocarriers.The synthesis of chiral nanographenes embedding [5]- or [7]helicenes is reported. Usually [5]helicenes are configurationally labile, while higher helicene homologs are stable. We synthesized a stable chiral nanographene with six embedded [5]helicene units (a [5]helicene trimer). We found a strong distortion of benzene rings, especially in the triphenylene core. The enantiomers were separated and the chiroptical properties were measured.The synthesis of [7]helicene trimer was also performed with a great enantio- and diastereoselectivity. When a Ni(0)- mediated cyclotrimerization is achieved with an enantiopure [7]helicene substrate, only one enantiomer of the trimer is obtained, while keeping intact the configuration of the substrate. On a racemic substrate, three diastereomers were obtained. One of them demonstrated the highest values of a benzene ring distortion reported to date (mean puckering angle and twisting angle).

O câncer de mama constitui o segundo tipo de câncer mais frequente no mundo e o mais comum entre as mulheres, devido ao seu alto grau de malignidade. A quimioterapia é utilizada no tratamento de câncer de mama com presença de metástase, dentre os fármacos mais utilizados está o paclitaxel, que atua na desestabilização dos microtúbulos na divisão celular, levando a célula neoplásica a apoptose, porém, o paclitaxel é uma molécula extremamente lipofílica, solubilizada em Cremophor® EL, um tensoativo altamente tóxico utilizado na formulação comercial. O objetivo deste trabalho foi desenvolver complexos dendriméricos com paclitaxel para a otimização da terapia do câncer de mama. Para a quantificação do paclitaxel nos sistemas de liberação desenvolvidos foram validados métodos analíticos por espectrofotometria UV-Vis e por cromatografia líquida de alta eficiência. Os métodos foram seletivos, linear, precisos e exatos. Para a obtenção de uma formulação concentrada os complexos foram liofilizados. O complexo PAMAM-G4-NH2-Paclitaxel foi obtido em diversos meios reacionais, com diferentes faixas de pH, sendo o tampão Hepes, pH 7,4, e água; os meios que obtiveram melhores resultados de complexação, posteriormente foram analisados por DLS e NTA, com diâmetro médio de partícula em 160 nm e potencial zeta catiônico. A caracterização do complexo obtido foi realizada por análises de espectrofotometria no infravermelho e ressonância magnética nuclear. O estudo in vitro de liberação do paclitaxel a partir dos complexos dendriméricos foi realizado utilizando membrana de acetato de celulose e quantificação por CLAE. O perfil de liberação demonstrou que após 156 horas, no máximo 35% do fármaco foi liberado. A liberação lenta representa uma vantagem para o tratamento de tumores sólidos, pois idealmente o sistema de liberação deve manter o fármaco encapsulado durante a circulação sanguínea e liberá-lo uma vez acumulado passivamente no sítio tumoral. A citotoxicidade foi avaliada na linhagem tumoral 4T1, através do ensaio do MTT. O complexo PAMAM-G4-NH2-Paclitaxel apresentou citotoxicidade 5 vezes maior que a formulação comercial. Na avaliação antitumoral in vivo do complexo, foram avaliados a curva do crescimento tumoral, o registro de peso, a sobrevivência dos animais e a proliferação celular com o anticorpo ki 67. O complexo dendrimérico teve efeito estatisticamente significativo na redução do volume tumoral e, através da análise de imunohistoquimica foi confirmada a redução da proliferação celular. Portanto, o complexo PAMAM-G4-NH2-Paclitaxel pode representar uma estratégia promissora para o tratamento de câncer de mama e posteriormente deverá ser avaliada por meio de estudos clínicos. / Breast cancer is the second most common type of cancer worldwide and the most common among women, due to its high degree of malignancy. Chemotherapy is used to treat breast cancer metastasis, among the most widely used drugs are paclitaxel, which operates in the microtubules destabilization in cell division, resulting in neoplastic cell apoptosis, however, paclitaxel is a highly lipophilic molecule which is solubilized in Cremophor® EL, a highly toxic surfactant used in the commercial formulation. The aim of this study was to develop dendrimeric complex with paclitaxel for the optimization of breast cancer therapy. To quantify the paclitaxel in the developed delivery systems, the analytical method was validated by UV-Vis spectrophotometry and high-performance liquid chromatography. The methods were selective, linear, accurate and precise. To obtain a concentrated formulation, the complexes were lyophilized. The PAMAM-G4-NH2-paclitaxel complex was obtained in various reaction media with different pH ranges, with the HEPES buffer, pH 7.4, and water. The media with obtained the best complexation were subsequently analyzed by DLS and NTA, and the mean particle diameter was 160 nm with a cationic zeta potential. The characterization of the obtained complex was performed by infrared and nuclear magnetic resonance spectrophotometric analysis. The in vitro release study of paclitaxel from the dendrimeric complex was evaluated using membranes of cellulose acetate and quantified by HPLC. The release profile showed that after 156 hours at most 35% of the drug was released. The extended release is an advantage for the solid tumors treatment, because ideally the release system should keep the drug encapsulated during blood circulation and release it over time passively accumulated in the tumor site. Cytotoxicity was assessed in tumor cell line 4T1, using the MTT assay, the PAMAM-G4-NH2 paclitaxel complex showed cytotoxicity 5 times greater than the commercial formulation. In in vivo antitumor evaluation of the complex were evaluated curve of tumor growth, the weight record, the animal survival and cell proliferation with the antibody ki 67. Dendrimer complex had statistically significant effect in reducing tumor volume and through the immunohistochemical analysis the results were confirmed the reduction of cell proliferation. Therefore, the PAMAM-G4- NH2-paclitaxel complex can represent a promising strategy for the breast cancer treatment and should be further evaluated by means of clinical studies

Les composés à base de lanthanides luminescents possèdent des propriétés uniques offrant de nombreux avantages pour l’étude de problèmes biologiques et pour le diagnostic. Ils résistent notamment à la photodécomposition, possèdent des temps de vie de luminescence longs ainsi que des bandes d’émissions étroites qui ne se recouvrent pas. De plus, certains lanthanides émettent dans le proche infrarouge, ce qui les rend particulièrement intéressants pour des applications d'’imagerie in vivo. De part l’interdiction des transitions f → f, les cations lanthanides ont des coefficients d’extinction très faibles. C’est la raison pour laquelle, il est nécessaire d’utiliser un ou plusieurs sensibilisateur(s) (comme un chromophore organique) pour exciter le lanthanide par « effet antenne ». Nous proposons ici de nouveaux composés émettant dans le proche infrarouge dont la structure permet d’incorporer une densité importante de lanthanides et de sensibilisateurs par unite de volume : i) les nano-MOF Yb-PVDC-3 constitués de chromophores dérivés de dicarboxylates de phenylènevinylène qui sensibilisent les cations Yb3+ du réseau. ii) les complexes formés avec des ligands dendrimères dérivés de polyamidoamine de génération 3 capables de sensibiliser 8 lanthanides (Eu3+, Yb3+, Nd3+) par le biais de 32 antennes dérivées du groupe 1,8-naphthalimide. La caractérisation physique, photophysique et la biocompatibilité de ces composés ont été réalisées. Ils ont montré une bonne stabilité dans différents environnements. Leur faible cytotoxicité a permis d’obtenir des images de microscopie proche infrarouge sur cellules vivantes. La preuve de principe que les nano-MOFs et les dendrimères complexant des lanthanides peuvent être utilisés comme rapporteurs luminescents in cellulo et in vivo a été ici établie. Les résultats obtenus valident la stratégie d’utiliser ce type de matériel pour augmenter le nombre de photons émis par unité de volume afin d’obtenir une meilleure sensibilité de détection. / Unique properties of luminescent lanthanides reporters explain their emergence for bioanalytical and optical imaging applications. Lanthanide ions possess long emission lifetimes, a good resistance to photodecomposition and sharp emission bands that do not overlap. In addition, several lanthanides emit in the near infrared (NIR) region of the electromagnetic spectrum making them very interesting for in vivo imaging. Free lanthanide cations have low extinction coefficients due to the forbidden nature of the f → f transition. Therefore, lanthanides must be sensitized using a photonic converter such as an organic chromophore through the “antenna effect". We report here new near-infrared emitting compounds whose structure allows to incorporate a high density of lanthanide cations and sensitizers per unit volume: i) nano-MOF Yb-PVDC-3 based on Yb3+ sensitized by phenylenevinylene dicarboxylates. ii) polymetallic dendrimer complexes formed with derivatives of new generation-3 polyamidoamine dendrimers. In these complexes, 8 lanthanide ions (Eu3+, Yb3+, Nd3+) can be sensitized by the 32 antenna derived from 1,8-naphthalimide. These two families of compounds were fully characterised for their physical, photophysical properties as well as for their biological respective compatibilities. They are stable in various media and their low cytotoxicity and emission of a sufficient number of photons are suitable for near-infrared live cell imaging. One of the main goal outcomes of this work is the establishment of the proof of principle that nano- MOFs and lanthanide derived dendrimers can be used for the sensitization of NIR emitting lanthanides to create a new generation of NIR optical imaging agents suitable for both in cellulo and in vivoapplications.The present work also validates the efficiency of the strategy to use both types of nanoscale systems described here to increase the number of emitted photons per unit volume for an improved detection sensitivity and to compensate for low quantum yields.

Au cours de cette thèse, nous avons synthétisé et caractérisé de nouveaux composés en utilisant le macrocycle porphyrinique comme brique moléculaire de départ. Le but de ce travail étant l’étude des propriétés optiques de ces nouveaux composés obtenus. Après avoir effectué l’étude bibliographique sur les porphyrines, nous avons fait une présentation générale des porphyrines symétriques et non symétriques, de leurs propriétés et de leurs synthèses. D’autre part, nous avons aussi considéré l’unité fluorène qui possède des propriétés photophysiques très intéressantes comme antenne collectrice de lumière. Puis, nous avons abordé des méthodes de synthèse permettant d’associer le macrocycle porphyrinique avec de nombreuses unités fluorènes. Cette association a pu être réalisée de différentes manières : soit de façon dendritique ou par connexion directe sur la porphyrine (dimère et trimère). Nous avons également décrit l’obtention d’une nouvelle famille de porphyrines substituées par des groupements organométalliques de type acétylure de ruthénium et de fer pour l’optique non linéaire de troisième ordre (ONL TO). Lors de la dernière partie de mes travaux de thèse, comme application de ces composés luminescents dans le rouge, nous avons reporté l’élaboration de différents dispositifs de diodes électroluminescentes (OLED) émettant dans le rouge. / During this thesis, we have worked on the synthesis and characterization of new compounds using the porphyrin macrocycle as a starting material. The aim, after synthesis, is to study the photophysical properties of these new molecules. A general bibliographic study was presented followed by introducing the synthetic methods of porphyrins and characterization means. Then, fluorene was considered to be an attracting unit due to its interesting photophysical properties: acting as efficient antennae for collecting light. First, we have presented the synthesis of porphyrin dendrimers having fluorenyl arms of different generations. That is to test the effect of number of fluorenes on the photophysical properties. Another way is to connect the fluorenes directly to the porphyrin core by synthesizing porphyrin dimer and trimer. We have also detailed the synthesis and characterization of a new family of porphyrin organometallic assemblies possessing ruthenium and iron moieties. In addition, a new organometallic porphyrin dendrimer bearing twelve ruthenium species was reported as well. These organometallic porphyrins are of interest in the third order of Nonlinear Optics (NLO). In the last chapter of this thesis we showed an example of application of porphyrin chemistry. We reported the elaboration of a new organic light emitting Diode (OLED) using these new porphyrins that emits in the red region.